Process and product relating to organic metal and metalloid containing complex compounds



mama Mar. 14, 1939 2,150,349

UNITED, STATES PATENT oFFrcs PROCESS AND PRODUCT RELATING TO ORGANIC LIETAL AND MIETALLOID' CON- TAININ G COIHPLEX COBIPOUNDS Adrianus Johannesvan Peski and Johannes Andreas, van Melsen, Amsterdam, Netherlands, assignors to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application April I0, 1936, Serial No. 73,710. In the Netherlands April 11, 1935 I Claims. (Cl. 260438) This invention relates to the production of valgarlic metal and metalloid-containing complex uable organic metal and metalloid-containlng compound is formed. complex compounds, and it further relates to a A valuable feature of the present invention is novel class of organic metal and metalloidconinherent in the simultaneous reaction of a mem- 5 taining complex compounds, which complex comber of one of the classes -01 compounds with at 5 pounds are adaptable to a wide variety of purleast one member selected from each of the other poses and which are particularly useful asmeans two classes. In accordance with the process of whereby metals in a soluble form can be introthe invention,- the necessity of first preparing duced into hydrocarbons and particularly hydroand isolating the organic metal compounds which carbon fractions, such as motor fuels, natural and it is desired to react with an organic metalloid in synthetic oils, lignite products, tar oils and the compound to obtain a metal and metalloid-conlike, for the purpose of improvingthese materials. taining complex organic compound of a prede- Three main groups or classes of compoundsare termined composition, is obviated. This is a very contemplated as reactants in accordance with the advantageous feature of the invention for the process of the invention. In apreferred embodireason that manyof the organic metal com- 15 ment of the invention one or more members sepounds, such as those which might be prepared lected from each of the classes of reactants hereby reacting a metal oxide, metal hydroxide or inafter described is caused to react simultanea metal saltof a weak acid with an organic comously with one or more members selected from pound containing a readily replaceable hydrogen each of the other two classes of reactants. atom, are extremely diflicult to prepare in prac- 0 The first class of reactants, hereinafter desigtical yields and in some cases cannot be prepared nated as the metal compounds", embraces the at all, in still other cases the organic metal commetal oxides, metal hydroxides and metal salts pounds may be so unstable as to render their use of weak acids. impractical and even dangerous. The advantages l The second class of reactants embraces organic inherent in the present invention are "clearly 25 compounds which possess one or a plurality of shown by the following example In the case that readily replaceable hydrogen atoms. The followit is desired to prepare, organic metal compound ing are representative types of compounds concomplexes with an organic phosphine, for examtemplated as members of this class: the organic ple, it is not always possible, or on account of acids, the alcohols, the phenols, acid amides, amthe dangers and difliculties attendant thereon, 30 ines, nitriles, aminoalcohols, phosphines, mercap desirable to prepare such organic metal and met tans, thioethers, the cyclodiolefines, acetylene, alloid-containing complexes by first preparing the acetylene homologues, and the like. organic metal compound and subsequently react- The third class of reactants embraces the oring it with the organic phosphine or otherorganic ganic compounds of the elements of the right metalloid compound. In many cases, the desired 35 hand side of groups V and VI which have an organic metal compound maybe unavailable or atomic number not less than fifteen, and the orit may be so unstable as to preclude its economical ganic compounds of the element nitrogen. A preuse. In accordance with the process of the presferred'subgroup of the compounds 01 this class entinvention these dlmculties are obviated and 40 includes the alkyl, aryl, aralkyl and cycloaliphatic by a suitable selection of readily available react- 40 compounds, as well as the substitution products ants of theclasses herein described any desired, thereof, of the metalloid elements phosphorus, organic metal and metalloid-containing complex arsenic, antimony, sulphur, selenium, tellurium compound can be prepared economicallyin a andnitrogen and the organic esters of the acids of practical yield.

5 these metalloid elements. As preferably employed specific members of the The process of the invention comprises effecting class of metal oxides, metal hydroxides and metal the simultaneous reaction of a compound of the salts of weak acids, the following come into conclass consisting of metal oxides, metal hydroxsideration: the alkali metal oxides, the alkali metides and metal salts of weak acids with an oral hydroxides, the alkaline earth metal oxides,

ganic compound containing one or a plurality of the alkaline earth metal hydroxides, aluminum 50 readily replaceable hydrogen atoms and with an hydroxides, aluminum oxide, cuprous oxide, cuprlc organic compound of an element of the right hand oxide, cupric hydroxide, cuprous hydroxide, silside of groups V and VI of the periodic table ver oxide, magnesium hydroxide, magnesium oxwhich has an atomic number not less than fifide, cadmium hydroxide, cadmium oxide, merteen, and the element nitrogen, whereby an orcuric hydroxide, mercuric oxide, mercurous ox 55 ide, thallium hydroxide, the thallium oxides, the zirconium oxides and hydroxides, the stannous and stannic oxides and hydroxides, the molyb-- platinum hydroxides. the platinum oxides, palladium hydroxide, the gold hydroxides, the gold oxides, and the like. Suitable metalsalts of weak acids include the alkali metal and alkaline earth metal carbonates and bicarbonates, copper car-, bonate, magnesium carbonate, the metal borates, the metal tetraborates, the metal salts of the organic acids of which sodium formate, sodium acetate, copper formate, copper acetate, copper propionate, copper butyrate, lead acetate, nickel formate, nickel acetate, nickel oleate and the like are representative.

Preferably, when metal salts of weak acids are used in the execution of the invention, the particular metal salt is selected with respectto the compound containing a readily replaceable hydrogen atom so that the compound in which the hydrogen atom is to be replaced by a metal atom has a stronger acid character than the weak acid from which the metal salt has been prepared.

The following compounds are representative organic-compounds which contain at least one readily replaceable hydrogen atom: the organic monobasic and polybasic-acids of saturated and unsaturated character as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, the valeric acids and homologues and suitable substitution products of these aliphatic acids, benzoic acid, cinnamic acid, maleic acid, malonic acid,

oxalic acid, lactic acid, succinic acid, the higherunsaturated acids as oleic, palmitic and the like; the saturated and unsaturated alcohols of monohydric as well as polyhydric character as methyl alcohol, ethyl alcohol, the propyl alcohols, primary butyl alcohol, secondary butyl alcohol, tertiary butyl alcohol, the amyl alcohols and the like, ethylene glycol, propylene glycol, the butylene glycols, the amylene glycols, diethylene glycol, dipropylene glycol, the dibutylene glycols, triethylene glycol, tripropylene glycol, glycerol, diglycerol, p-methyl glycerol, di-p-methyl glycerol, erythritol and the'like and their homologues, analogues and suitable substitution products. The unsaturated alcohols as allyl alcohol, crotyl'alcohol, isobutenol, cinnamyl alcohol, propargyl alcohol and the like are also suitable. Suitable phenolic bodies include phenol, the cresols, hydroquinone, pyrogallol, the naphthols, the xylenols and the like. Representative acid amides are formamide, ethanamide, propanamide, the butanamides, etc., and their homologues and analogues. The amines of primary, secondary and mixed character are suitable, the following being representative members: methyl amine, dimethyl amine, ethyl amine, diethyl amine, methyl ethyl amine, the propyl monoamines, the propyl-diamines, analine, phenylene diamine, ethylene diamine, and the like and their homologues and suitable substitution products. The nitriles are represented by the following aliphatic, aromatic and aralkyl compounds: aceto-nitrile, propionitrile, butyro-nitrile, valeromitrile, palmitonitrile, methyl isocyanide, ethyl isocyanide, benzonitrile, benzyl cyanide and the like. Suitable amino-alcohols include the mono-, diand trimethanolamines, monoethanolamine, triethanolamine, diethanolamine, the monoand polypropanol amines, methyl amino-propanol and the like and their homologues, analogues and suitable substitution products. Suitable phosphines include "methyl phosphine, dimethyl phosphine, ethyl phosphine, diethyl phosphine, propyl phosphine, butyl phosphine, phenyl phosphine, benzyl 'phosphine and the like. Suitable mercaptans include the saturated and unsaturated alkyl and aralkyl mercaptans and the aromatic and other cyclic mercaptans as methyl mercaptan, ethyl mercaptan, the propyl mercaptans, allyl mercap tan, crotyl mercaptan, isobutenyl mercaptan, the

butyl mercaptans, benzyl mercaptan,-phenyl mercaptan and the like and their homologues. Suitable hydrocarbons whichcontain readily replaceable hydrogen atoms include, among others, the alkadienes, as butadiene, pentadiene, hexadiene, etc., and particularly the cycloalkadienes as cyclobutadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene and the like and compounds containing an acetylenic linkage as acetylene and its homologues as methyl acetylene and the like and other suitable hydrocarbons containing readily replaceable hydrogen atoms.

Examples of suitable substituted and non-substituted alkyl, aralkyl, aryl and cycloaliphatic compounds of the elements of the right hand side of groups V and VI of the periodic table which have an atomic number not less than 15, and the element nitrogen and the esters of acids of these compounds, are pyridine, ethyl amine, ethyl diamine, ethyl triamine, the methyl, propyl, butyl and the higher amines, the mixed amines as ethyl propyl amine, aniline, ethylene diamine, phenylene diamine, ethanolamine, diethanolamine, triethanolamine, propanolamine, aminoacetic acid, aminobutyric acid, ethyl carbylamine, propyl carbylamine, phenyl carbylamine, aceto-nitrile, propio-nitrile, butyro-nitrile, trimethyl phosphine, triethyl phosphine, tripropyl phosphine, tributyl phosphine, tribenzyl phosphine, triphenyl phosphine, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, trimethyl stibine, triethyl stibine, tripropyl stibine, tributyl stibine, methyl ethyl sulphide, dimethyl sulphide, diethyl sulphide, dipropyl sulphide, dibutyl sulphide, S-ethyl thioglycollic acid ethyl ester, ethylene diethyl sulphide, propylene diethyl sulphide, diethyl disulphide, dimethyl selenium, diethyl selenium, dipropyl selenium, dibutyl selenium, allyl sulphide, isobutenyl sulphide, dimethyl tellurium, trimethyl arsine, triethylarsine, bismuth trimethyl, diethyl tellurium and the like and their homologues, analogues and suitable substitution products.

The reaction may be effected with any suitable proportion of the reactants depending upon the particular operation and the particular complex compound desired. In some cases it is desirable to exe'cute the invention with the reactants present in the reaction mixture in equivalent amounts or with the other reactants in excess of the metal oxide, metal hydroxide or metal saltof a weak acid so as to facilitate conversion of the latter.

The reaction is preferably effected in a reaction vessel equipped with suitable heating and cooling means and means for agitating the reaction mixture as by shaking or mechanical stirring. The reactants may be introduced into the reaction vessel in any desirable manner and order provided that the reactants are present in the reaction mixture at sucha time and in such amounts that simultaneous reaction of the three classes of reactants occurs. The reaction may be effected at any desired temperature and pres- About 13.5 gm. of tri-n-propyl phosphite were heated with about 3.0 gm. of nickel hydroxide and about 3.9 gm. of formaniline in a nitrogen atmosphere at a temperature of about 170 C. to 180 C. for about 3 hours. At the end of this time the mixture was added to 1 liter of a benzine substantially free of aromatic hydrocarbons and the mixture shaken for about 12 hours. The mixture was then filtered and the filtrate analyzed. It contained more than 0.2% of Ni, boundv in a double :compound of the formula nicumiomaz (CaH'zO) 3? EXAMPLE VI Preparation of cupro-cyclopentadiene-tri-normal prom/l phosphzne (CuC'5H5.2(C3H7) 3P) A mixture consisting of about 29 gm. of tri-npropyl phosphine, about 6.5 gm. of cuprous oxide, about 6.0 gm. of cyclopentadiene and about 20 c. c. of benzol was charged to a suitable reaction vessel, put under a nitrogen atmosphere, and heated to the boiling temperature of the mixture for about 2 hours. A clearly perceptible reaction took place, as indicated by water formation and the gradual consumption of the solid cuprous oxide. At the end of two hours of treatment the mixture was cooled and'filtered. About 2.5 gm. of unreacted cuprous oxide were filtered from the mixture. The filtrate was evaporated to remove the lower boiling constituents. The residue, about 34.4 gm. being obtained, was found to have the formula CuC5Hs.2(C3H7)3P. This complex organic metal compound is readily soluble in benzine fractions, particularly in those fractions substantially free of aromatics.

Other representative examples of valuable organic metal and metalloid complex compounds, which may be readily prepared in good yield in accordance with the process of our invention, are

the following:

Cupro-acetateethylene diamine cuoocomolnlmm Cupro-urea-triethyl phospliine CuNHC ON Hz.(C:Hs)aP Dicupro-urea-triethyl phosphine Cu2NCONH2-(C2H5)3P stg n cresolate-triethyl phosphite Sn (0C5H5CH3).(C,H;O);P Ferri-phcnolatetriethyl phosphite F6(OCuH5)3-(C:H5O)3P When a compound of the class consisting of metaloxides, metal hydroxides and salts of weak acids is simultaneously reacted with a compound of the class consisting of alcohols, acid amides,

amines, nitriles, aminoalcohols, phosphines, mercaptans, alkadienes, cycloalkadienes, acetylene and acetylene homologues and with an organic metalloid compound of the class consisting of the hydrocarbon and substituted hydrocarbon compounds of the elements'of the right hand side of groups V and VI of the periodic table which have an atomic number not less than 15, and the element nitrogen, and the organic esters of acids of these elements, the resulting organic metal and metalloid-containing complex compounds are novel.

The members of this novel class of organic metal and metalloid-containing complex compounds may be represented by the general for-' mula (MR) .arZ, wherein (MR) represents the compound of a. metal with an organic compound of the class consisting of alcohols, acid amides, amines, nitriles, aminoalcohols, phosphines, mercaptans, alkadienes, cycloalkadienes, acetylene and acetylene homologues, and Z represents an organic metalloid compound of the class consisting of the hydrocarbon and substituted hydrocarbon compounds of,-and the organic esters of acids of, the elements of the right hand side of groups V and VI of the periodic table which have an atomic number not less than 15, and the element nitrogen, :1; representing an integer not usually greater than 2.

A valuable subgroup of novel organic'metal and metalloid-containing complex compounds embraces the double compounds of metal salts of organic acids and phenolic compounds with substituted or non-substituted alkyl, aralkyl, aryl and cycloaliphatic compounds of phosphorus, arsenic, antimony, sulphur, selenium and tellurium or with organic esters of acids of these elements.

Another subgroup of novel organic metal and metalloid-containing complex compounds embraces the, double compounds of inorganic metal salts, exclusive of the metal halides, with substituted or non-substituted alkyl, aralkyl, aryl and cycloaliphat ic compounds of phosphorus, arsenic, antimony, sulphur, selenium and tellurium or with organic esters of acids of these elements.

The organic metal and metalloid-containing complex compounds are useful for a wide variety of purposes. They are of particular value as means of introducing metals in a soluble and ac tive form into hydrocarbons and hydrocarbon mixtures, particularly motor fuels and lubricating oil compositions for the purpose of enhancing the value of such hydrocarbon materials and making them more suitable for special purposes.

The great majority of the organic complex compounds which are prepared in accordance with the process of the invention are readily soluble to a considerable extent in a wide variety of organic solvents. They are even readily soluble in the non-polar and slightly polar solvents such as tar oil products (benzol and its homologues), petroleum fractions as kerosene, gasoline, gasoil, lubricating oils and the like, hydrogenation products of olefine polymers, coal, tar, mineral oils, shale oils, etc., cracking products of tars, waxes, mineral oils, animal oils, vegetable oils and the like carbonaceous materials. Consequently, the organic metal and metalloid-containing complex compounds may be dissolved in the required amount in a hydrocarbon material, or suspended in such a hydrocarbon material, to improve it in some desired respect. Many of the organic metal complex compounds when added to motor fuels as gasoline, iso-octane, etc., improve the anti-knock properties of the fuels or fuel mixtures. The organic metal complex compounds also act as anti-oxidants, and when added to lubricating oils and greases render them suitable as extreme pressure lubricants.

While we have in the foregoing described in some detail the preferred embodiment of our invention and some variants thereof, it will be understood that this is only for the purpose of making the invention more clear and that the same is not to be regarded as limited to the details of operation described nor is it dependent upon the soundness or accuracy of the theories which we have advanced as to the advantageous results attained. On the other hand, the invention is to be regarded as limited only by the terms and metalloid-containing complex organic compounds which comprises bringing together and simultaneously reacting at least three difierent reactants, one reactant being ametal compound of the class consisting of the metal oxides and metal hydroxides, another reactant being an organic compound containing a readily replaceable hydrogen atom but devoid of any acidforming multivalent element of groups V and. VI of the periodic table which has an atomicity greater than one and an atomic number not eater than 52, and the third reactant being an organic compound of an acid-forming multivalent element of groups V and VI of the periodic table which has an atomicity greater than one and an atomic number not greater than 52.

2. A process for the production of useful metal and metalloid-containing complex organic compounds which comprises bringing together and simultaneously reacting, in the liquid phase and in the presence ofa substantially inertnormally liquid diluent material, at least three different reactants, one reactantbeing a metal compound of the class consisting of the metal oxides and metal hydroxides, another reactant being an organic compound containing a readily replaceable hydrogen atom but devoid of any acid-forming multivalent element of groups V and VI of the periodic table which has an atomicity greater than one and an atomic number not greater than 52, and the third reactant being an organic compound of an acid-forming multivalent element of groups V and VI of the periodic table which has an atomicity greater than one and an atomic number not greater than 52.

3. A process for the production of useful metal and metalloid-containing complex organiccompounds which comprises bringing together and simultaneously reacting at least three different reactants, one reactant being a metal oxide, another reactant being an organic compound containing a readily replaceable hydrogen atom but devoid of any acid-forming multivalent element of groups V and VI of the periodic table which has an atomicity greater than one and an atomic number not greater than 52, and the third reactant being an organic compound of an acidforming multivalent element of groups V and VI of the periodic table which has an atomicity greater than one and an atomic number not greater than 52.

4. A process for the production of a useful copper and metalloid-containing complex organic compound which comprises bringing together and simultaneously reacting at least three different reactants, one reactant being a copper oxide, another reactant being an organic compound containing a readily replaceable hydrogen atom but devoid of any acid-forming multivalent element of groups V and VI of the periodic table which has an atomicity greater than one and an atomic number not greaterthan 52, and the third re actant being an organic compound of an acidforming multivalent element of groups V and VI of the periodic table which has an atomicity greater than one and an atomic number not greater than 52.

5. A process for the production of useful metal and metaJloid-containing complex organic com-' pounds which comprises bringing togetherand simultaneously reacting at least three different reactants, one reactant being a metal compound of the class consisting of the metal oxides and metal hydroxides, another reactant being an organic hydroxy compound but devoid of any acidforming multivalent element of groups V and VI of the periodic table which has an atomicity greater than one and an atomic number not reater than 52, and the third reactant being an organic compound of an acid-forming multivalent element of groups V and VI of the'periodic table which has an atomicity greater than one and an atomic number not greater than 52.

6. A process for the production of useful metal and metalloid-containingcomplex organic compounds which comprisesbringing together and simultaneously reacting at leastthree different reactants, one reactant being a metal compound of the class consisting of the metal oxides and metalhydroxides; another reactant being an organic compound containing a readily'replaceable hydrogen atom but devoid of any acid-forming multivalent elementof groups V and VI of the periodic table which has an atomicity greater than one and an atomic number not greater than 52,. and the third reactant being an organic compoundof the class consisting of the alkyl, aralkyl and aryl compounds of acid-forming multivalent elements of groups Vand VI of the periodic table whichhave an atomicitygreater than one and an atomic number not greater than 52. I

7. A process for the production of useful metal and metalloid-containing complex organic compounds which comprises bringing together and simultaneously reacting at least three different reactants, one reactant being a metal, compound of the class consisting of the metal oxides and metal hydroxides, another reactant being an organic compound containing a readily replaceable hydrogen atom but devoid of any acid-forming multivalent element of groups V and VI of the periodic table which has an atomicity greater than one and an atomic number not greater than 52, and the third reactant being an alkyl compound of an acid-forming multivalent element of groups V and VI of the periodic table which has an atomicity greater than one and an atomic number not greater than 52.

8. A process for the production of useful metal and metalloid-containing complex organic compounds which comprises bringing together and simultaneously reacting at least three diiierent reactants, one reactant being a metal compound of the class consisting of the metal oxides and metal hydroxides, another reactant being an organic compound containing a readily replaceable hydrogen atom, and the third reactant being an alkyl ester of an inorganic acid of an acid-forming multivalent element of groups V and VI of the periodic table which has an atomicity greater than one and an atomic number not greater than 52.

9. A process for the production of useful metal and metalloid-containing complex organic compound which comprises bringing together and simultaneously reacting at least three different reactants, one reactant being a metal compound of the class consisting of the metal oxides and metal hydroxides, another reactant being an organic compound containing a readily replaceable hydrogen atom but devoid of phosphorus, and the third reactant being an organic compound of phosphorus.

10. A process for the production of cuprobutyrate-diethyl sulphide'of the formula CuOOCCsHv. (Col-I) 23 which comprises reacting cuprous oxide simultaneously with butyric acid and with diethyl sulphide, the reaction being elfected in the liquid phase in a substantially inert non-oxidizing atmosphere.

11. The metal and metalloid-contaim'ng coinplex organic compounds of the generaliormula (MR) .acZ, the group MR representing an organic compound wherein a readily replaceable hydrogen atom has been replaced by a metal radical, Z representing an organic compound of anacidforming multivalent element of groups V and VI of the periodic table whichihas an atomicity greater than one and an atomic number. not greater than 52, and :1: representing an integer not greater than two, the compound Z, being bound to the group MR to form a metal-containing complex organic compound. 7'

12. The metal and metalloid-containinglcomr plex organic compounds of the general .formula (MR) .xZ, the group MR representing the metal salt of an organic acid, Z representing'an organic compound of an acid-forming multivalent elesenting an integer not greater than two, the compound Z being bound to the group MR to form a metal-containing complex organic compound.

13. The complex compound: cuprob utyratediethyl sulphide of the formula 14. The copper-containing complex organic compound of the general formula (l\/IR).:|:Z, wherein MR represents the copper salt of a carboxylic acid, n: represents an integer not greater than two, and Z represents an alkyl compound of "an acid-forming multivalent element of groups V and VI of the periodic table which has an atomicity greater than one and an atomic number not greater than 52, Z being bound to MR to form a copper-containing complex organic compound.

v 15. The metal and metalloid-containing com-= plex organic compound of the general formula (MR) .rZ, the group MR representing an organic compound devoid of phosphorus and wherein a readily replaceable hydrogen atom has been replaced by a metal radical, X representing an integer not greater than two and Z representing i 

